WO2022235126A1 - 분리막용 다공성 기재 및 이를 포함하는 전기화학소자용 분리막 - Google Patents
분리막용 다공성 기재 및 이를 포함하는 전기화학소자용 분리막 Download PDFInfo
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 238000003618 dip coating Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- 239000008169 grapeseed oil Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 229910052747 lanthanoid Inorganic materials 0.000 description 1
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- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical group [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical group [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
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- 229920006393 polyether sulfone Polymers 0.000 description 1
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- 238000002459 porosimetry Methods 0.000 description 1
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- 238000009824 pressure lamination Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- KBEVZHAXWGOKCP-UHFFFAOYSA-N zinc oxygen(2-) tin(4+) Chemical class [O--].[O--].[O--].[Zn++].[Sn+4] KBEVZHAXWGOKCP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a separator for an electrochemical device, and the electrochemical device may be a primary battery or a secondary battery, and the secondary battery may include a lithium ion secondary battery.
- Polyolefin microporous membranes are widely used for battery separators including lithium batteries, diaphragms for electrolytic capacitors, moisture-permeable waterproof clothing, and various filtration membranes.
- battery separators including lithium batteries, diaphragms for electrolytic capacitors, moisture-permeable waterproof clothing, and various filtration membranes.
- polyolefin microporous membrane When such a polyolefin microporous membrane is used as a battery separator, its performance is closely related to battery characteristics, productivity, and safety.
- a microporous film formed only of polyethylene has a low meltdown temperature
- a microporous film formed only of polypropylene has a high shutdown temperature. Accordingly, a battery separator formed of a microporous film mainly composed of polyethylene and polypropylene has been proposed.
- Japanese Patent No. 3235669 discloses at least one first layer formed of a polymer selected from low-density polyethylene, an ethylene-butene copolymer, or an ethylene-hexene copolymer as a battery separator having excellent heat shrinkage resistance and shutdown characteristics, and a high density
- a battery separator having at least one second layer formed of a polymer selected from polyethylene, ultra-high molecular weight polyethylene or polypropylene is disclosed.
- Japanese Patent No. 3422496 discloses a battery separator having excellent shutdown properties, comprising at least one first layer formed of a polymer selected from ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-methacrylate copolymer, or polyethylene; or a battery separator having at least one second layer formed of a polymer selected from polypropylene.
- Japanese Patent No. 2883726 describes a battery separator with excellent shutdown and meltdown properties, by simultaneously extruding polypropylene having a melting point of 150° C. or higher and polyethylene having a melting point of 100° C. to 140° C.
- a battery separator formed by uniaxial stretching at a temperature of melting point (Tm0)-30]°C and further stretching in the same direction at a temperature of (Tm0-30)°C to (Tm0-2)°C to make it porous is disclosed. .
- a battery separator with excellent shutdown characteristics and strength is formed of a two-layer polypropylene microporous strength layer and a barrier layer made of polyethylene material containing filler interposed therebetween, and polyethylene material containing filler material.
- a battery separator in which the blocking layer is formed of a microporous film produced by a particle stretching method has been proposed.
- a battery is manufactured by bonding such a separator to an electrode, and the bonding is performed by a lamination process in which heat and/or pressure are applied after laminating the electrode and the separator.
- the process speed is increased and the time that heat is applied to the separator is short, so the adhesive force is secured by increasing the pressure to secure the adhesive force, but there is a problem in that the separator is deformed by the high pressure.
- An object of the present invention is to provide a porous substrate for a separator having a low thickness strain and a high dielectric breakdown voltage, and a separator including the same. It will be readily apparent that the objects and advantages of the present invention may be realized by means or methods and combinations thereof recited in the claims.
- the present invention relates to a porous substrate for a separator, wherein the porous substrate includes polyethylene and/or polypropylene, and the substrate has a porous property including a plurality of pores therein, and its porosity is 30 vol% to 60 vol% , and the dispersion of the pores means that the value of the full width at half maximum (FWHM) of the Gaussian pore distribution measured through the distribution of the pore side distribution is 2.0 nm or less.
- FWHM full width at half maximum
- the dispersion of the pores has a value of half maximum width of 1.5 nm or less.
- the difference between the maximum pore size (Mps) and the average pore size (mps) is 30 nm.
- the difference between the maximum pore size (Mps) and the average pore size (mps) is 20 nm.
- the average pore size (mps) is 10 nm to 100 nm.
- the average pore size (mps) is 20 nm to 30 nm.
- a seventh aspect of the present invention in any one of the first to sixth aspects, wherein the porous substrate has a BET of 20m 2 /g to 60m 2 /g.
- the porous substrate has a thickness of 5 ⁇ m to 20 ⁇ m.
- a ninth aspect of the present invention relates to a separator for an electrochemical device, wherein the separator is a porous substrate for a separator according to any one of the first to eighth aspects and one or both sides of the surface of the porous substrate and a heat-resistant layer formed thereon, wherein the heat-resistant layer includes a binder resin and inorganic particles.
- a tenth aspect of the present invention relates to an electrochemical device, comprising a cathode, an anode, and a separator interposed between the cathode and the anode, wherein the separator is according to the ninth aspect.
- the porous substrate according to the present invention has a small pore size and a uniform pore distribution, and when applied to a separator, when the separator and the electrode are laminated and put into a lamination process, the thickness deformation is small and the dielectric breakdown voltage is high.
- FIG. 1 is a cross-section of a porous substrate of a comparative example, schematically showing a deformed state due to compression.
- Figure 2 is a cross-section of the porous substrate of the embodiment schematically shows the deformation state due to compression.
- 3 exemplarily shows a Gaussian distribution of pores for confirming the half-maximum width of the pore size.
- the present invention relates to a porous substrate that can be applied to a separator for an electrochemical device.
- the electrochemical device is a device that converts chemical energy into electrical energy by an electrochemical reaction, and is a concept including a primary battery and a secondary battery, and the secondary battery is capable of charging and discharging.
- a lithium ion battery a nickel-cadmium battery, a nickel-hydrogen battery, and the like.
- the separator serves as an ion-conducting barrier to pass ions while blocking electrical contact between the cathode and the anode in the electrochemical device. It is preferable that a plurality of pores are formed therein, and the pores are interconnected to each other, so that gas or liquid can pass through one side of the separation membrane to the other side.
- the separator according to the present invention includes a porous substrate made of a polymer material including a plurality of pores.
- another layer may be additionally disposed on at least one surface of the porous substrate in terms of material or function, if necessary.
- the separation membrane may include the porous substrate and the heat-resistant layer, for example, the heat-resistant layer may be formed on at least one surface of the porous substrate.
- the heat-resistant layer may include inorganic particles and/or a binder resin.
- the inorganic particles in the heat-resistant layer may have a layered structure in which they are bound by a binder resin, and the porosity resulting from the space (interstitial volume) formed between the inorganic particles. structure can be shown. This porous structure has the effect of improving the electrolyte retention of the separator.
- the separator when the separator includes a heat-resistant layer, the separator may have a heat-resistant layer of 3 vol% to 40 vol% with respect to 100 vol% of the total total volume, , at the same time or independently, the heat-resistant layer may be 5% to 50% compared to 100% of the total thickness of the separator.
- the porous substrate may have a form of a porous sheet including a polymer resin and having a plurality of pores.
- the pores include open pores, and the open pores have a structure connected to each other so that gas or liquid can pass through one side of the porous substrate to the other side.
- the porous substrate preferably has an air permeability of 2000 sec/100ml or less and a porosity of 30 vol% to 60 vol% in terms of output and cycle characteristics of the battery.
- the air permeability refers to the time (seconds) it takes for 100 ml of air to pass through a sample such as a porous substrate or a separator having a size of 1 square inch under a constant air pressure.
- the air permeability may be measured according to standard regulations in the art.
- the air permeability may be measured using a known Gurley Densometer according to ASTM D 726-58 or ASTM D726-94, for example, air at a pressure of 0.304 (kPa) or 1.215 It can be the time in seconds for 100 ml of air to pass through a sample of 1 square inch (or 6.54 cm 2 ) under a pressure of kN/m 2 water.
- the air permeability is measured according to the Gurley measurement method of the Japanese industrial standard (JIS-P8117), under a constant pressure of 4.8 inches H 2 O at room temperature, it takes 100 ml of air to pass through a sample of 1 square inch. It can be expressed in hours (seconds).
- the air permeability may be measurable using, for example, Asahi seico EG01-55-1MR equipment according to the above standard regulations.
- the porosity refers to the ratio of the volume occupied by the pores to the total volume, vol% is used as its unit, and can be used interchangeably with terms such as porosity and porosity.
- the measurement of the porosity is not particularly limited, and a method known in the art may be applied. For example, BET (Brunauer-Emmett- Teller) measurement method using nitrogen gas, water intrusion prosimeter method, capillary flow porometer (capillary flow porometer) or mercury infiltration method (Hg porosimeter) can be measured.
- BET Brunauer-Emmett- Teller
- the true density of the porous substrate is calculated from the density (apparent density) of the obtained porous substrate, the composition ratio of the materials included in the porous substrate, and the density of each component, and the apparent density and
- the porosity of the porous substrate can be calculated from the difference in net density.
- the porosity can be calculated by [Equation 1] below.
- the porous substrate has a small and uniform pore size, and when applied to a separator for an electrochemical device, excellent shape stability and withstand voltage characteristics can be exhibited.
- the maximum pore size (Mps) of the porous substrate is 80 nm or less, and the difference between the maximum pore size (Mps) and the average pore size (mps) is 30 nm or less, preferably 20 nm or less.
- the average pore size (mps) preferably has a range of 10 nm to 100 nm.
- the size of the pores may be calculated from a pore size distribution measured using a capillary flow porometer method.
- the capillary flow porometer may be measured using a porometer of Porous Materials Inc. and a galwick solution, and the measurement method described below may be referred to.
- the relationship between air pressure and flow rate is measured using a porometer for each of the porous substrate in a dry state (dry sample) and the porous substrate in a wet state (wet sample), and as shown in FIG. 4, the airflow curve of the dry sample ( A dry curve, a dry curve) and an aeration curve (wet curve) of a wet sample can be obtained, and the size and distribution of pores can be confirmed therefrom.
- the porous substrate is wetted using a wetting solution with low surface tension and then pressurized using a gas to push out the wetting solution filling the pores of the porous substrate. to measure the pore size.
- a wetting solution such as a galwick solution
- the air pressure on one side of the porous substrate is gradually increased.
- the applied air pressure is greater than the capillary attraction of the wetting liquid existing in the pores, the wetting liquid blocking the pores is pushed out, and the pore size and distribution can be measured through the pressure and flow rate at the moment of expulsion.
- a non-reactive gas may be used in place of the air.
- the measurement may be measured in a measurement pressure range of 0 to 3500 MPa, and the minimum air pressure within the range may be 30 psi or more, and the maximum air pressure may be 500 psi or less.
- the minimum air pressure may mean a bubble point pressure.
- the bubble point refers to the pressure at the starting point at which the pressure curve is drawn in the capillary flow porometer, and may reflect the maximum pore size among the pore diameters of the porous substrate. That is, when the air pressure is gradually increased, the wetting liquid filled in the pores of the separator substrate is pushed and moved by the pressure in the order of the pores having a larger diameter. Accordingly, the air flow rate is gradually increased and the sample is finally dried.
- the pressure at the starting point at which the wetting liquid moves is called the bubble point pressure.
- the maximum air pressure may be the pressure when the sample is finally dried, and may reflect the minimum pore size.
- the maximum air pressure may mean a pressure at a point where the pressure curve (wetting curve) of the capillary flow porometer measured using the wetting liquid meets the aeration curve of the dry sample.
- the 'dry curve of the dry sample' is the pressure distribution required to pressurize the membrane substrate in a dry state that is not infiltrated with the wet liquid using air or a non-reactive gas to push out the existing gas filling the pores.
- FIG. 4 shows a pressure curve of a wet sample and a pressure curve of a dry sample using a capillary flow porometer. The point where the pressure curve of the wet sample and the pressure curve of the dry sample meet is the maximum air pressure. have.
- the diameter of the pores can be calculated.
- Equations 3 to 5 it is possible to obtain a pore size distribution curve showing the relationship between the pore diameter D and the pore diameter distribution PSF based on the pressure change of the air flow rate in the dry state and the wet state.
- An example of such a pore diameter distribution curve is shown in FIG. 3 .
- Various physical property values regarding pores can be obtained from the pore diameter distribution curve shown in FIG. 3 .
- the bubble point may represent the maximum diameter of the pore, and the point where the wet sample curve and the dry sample curve meet may represent the minimum diameter of the pore.
- a point at which the aeration curve of the 1/2 dry sample and the wet sample curve, which is a value corresponding to 1/2 of the value of the aeration curve of the dry sample, may represent the average value of the pore diameter (see FIG. 4 ).
- the porous substrate has a full width at half (FWHM) in a pore diameter distribution (see FIG. 3) according to a normal distribution (Gaussian distribution) measured through the pore size distribution.
- maximum peak height is 4.0 nm or less, or 3.0 nm or less, 2.0 nm or less, or 1.5 nm or less. Preferably, it may be 3.0 nm or less.
- the half width is defined as the size difference between two points on the x-axis that is half of the maximum value (mode among pore sizes) on the y-axis in the normal distribution for the pore size distribution shown by classifying the pores formed inside the porous substrate according to their sizes.
- the x-axis represents the size (diameter) of the pores
- the y-axis represents the frequency of the number of pores corresponding to the size of the pores on the x-axis (the number of pores or the percentage of the number of pores, etc.).
- the unit of the x-axis may be expressed in nm or ⁇ m.
- the full width at half maximum (FWHM) may be expressed as a difference between two points X 2 and X 1 on the x-axis corresponding to 1/2 (1/2T) of the y-axis mode T.
- the difference may be expressed as an absolute value.
- the normal distribution may represent symmetric and asymmetric, and arbitrary distributions other than normal with respect to a maximum value.
- the full width at half maximum may be determined from the distribution of pores other than the pores having the largest diameter.
- the shape of the pores may be circular, oval, or amorphous, and the cross-section may be a closed curve.
- the diameter of the pores means the longest length among the distances between any two points in the closed curve.
- the porous substrate preferably has a BET surface area of 20 m 2 /g to 60 m 2 /g.
- the larger the BET surface area the higher the porosity and the smaller the pore size. Also, at the same porosity, the smaller the pore size, the larger the BET surface area.
- the BET surface area can be measured using the adsorption equation of the BET (Brunauer, Emmett, and Teller) model. It can be calculated by measuring the adsorption amount from the N 2 adsorption isotherm.
- the porous substrate may have a thickness of 5 ⁇ m to 20 ⁇ m in terms of thin film and high energy density of the electrochemical device.
- the thickness of the porous substrate does not fall within the above numerical range, the function of the conductive barrier is not sufficient, whereas when the thickness of the porous substrate exceeds the above range (ie, too thick), the resistance of the separator may excessively increase.
- the polymer resin may include a thermoplastic resin having a melting point of less than 200 ° C. .
- the shutdown function refers to a function of preventing thermal runaway of the battery by blocking the movement of ions between the positive and negative electrodes by melting the polymer resin and closing the pores of the porous substrate when the battery temperature increases.
- polystyrene-based resin examples include polyethylene, polypropylene, polybutene, and polypentene, and may include one or a mixture of two or more of them.
- the polyolefin-based resin may include two or more selected from polyethylene, polypropylene, and polypentene.
- the polyolefin-based resin may be polyethylene and/or polypropylene.
- the porous substrate includes a base polyethylene, and polypropylene may be included if necessary.
- the content of polypropylene is 0 wt% to 5 wt% compared to 100 wt% of the base material.
- the content of polypropylene may be less than 5 wt%.
- the polyethylene may have a weight average molecular weight (Mw) of 300,000 g/mol to 1,800,000 g/mol, preferably 300,000 g, in terms of implementing a compression ratio range to be described later. /mol to 1,500,000 g/mol, or 300,0000 mol to 1,000,000 mol or 300,000 mol to 500,000 mol.
- the polyolefin-based resin is preferably included at least 90wt% or 95wt% of 100wt% of the polymer material.
- the polyolefin-based resin may include, for example, one or a mixture of two or more selected from the group consisting of polyethylene, polypropylene, polybutene, and polypentene.
- the polyolefin-based resin may be polyethylene and/or polypropylene.
- the polymer resin preferably has a poly dispersity index (PDI) value in the range of 2.5 to 6.5.
- the mixed polymer resin may satisfy the above PDI.
- the polymer resin contains more than 50 wt%, 70 wt% or more, or 90 wt% or more of any one type of polymer resin as a single component relative to 100 wt% of the polymer material within the range satisfying the PDI.
- the polymer resin may be formed of only a single component.
- the single component means that the chemical structure (particularly, repeating unit) of the polymer resin is the same and the PDI satisfies the range of 2.5 to 6.5.
- 90 wt% or more of polyethylene having a PDI of 2.5 to 6.5 compared to 100 wt% of the polymer material may be included or may be composed of only these.
- the polydispersity index may be obtained from a ratio of number average molecular weight (Mn)/weight average molecular weight (Mw).
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) may be measured by gel permeation chromatography (GPC, PL GPC220, Agilent Technologies), and the measurement conditions are as follows. can be set.
- the polymeric material may have a Melting Index (MI) in the range of 0.02 g/10min to 1.0 g/10min.
- MI Melting Index
- the MI is based on a condition in which a load of 21.6 kg is applied at 190°C.
- the porous substrate may include polypropylene, but the content of polypropylene in the porous substrate is preferably controlled to be 5 wt% or less, for example, less than 5 wt%.
- the higher the polypropylene content the lower the crystallinity of the polymer. Accordingly, even if the porosity is high and the penetration strength is low, the compressibility or permanent set does not decrease, and the Hi-Pot defect rate, which is a withstand voltage characteristic, can be maintained low.
- the content of polypropylene exceeds the above range, when the porous substrate is prepared by the wet method, it is chemically unstable and thus pores are not well formed, which is disadvantageous for the development of porous properties. It is preferable to do
- the porous substrate may include polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, Polyphenylene oxide, polyphenylene sulfide, may further include at least one of a polymer resin such as polyethylene naphthalene.
- the porous substrate of a polymer material satisfying the above thickness range may be manufactured through a wet manufacturing method by applying polyethylene.
- the porous substrate may be a porous polymer film prepared in the manner described below, and may be a single-layer film or a multi-layer film formed by laminating two or more sheets.
- the separator satisfying the above values has improved withstand voltage characteristics of the battery, so that the breakdown voltage is increased and the short circuit occurrence rate (Hi-Pot defect rate) is reduced even under high voltage conditions.
- the breakdown voltage is the highest voltage that an insulator can withstand
- dielectric breakdown means that when a voltage is applied to an insulator, when a voltage is higher than a certain value, the insulation is destroyed and insulation performance is lost.
- the withstand voltage characteristic can be confirmed by a method of measuring the breakdown voltage of the separator, which is to measure the voltage at which dielectric breakdown occurs by placing a separator that is an insulator between two conductors and applying a voltage. method can be checked.
- This breakdown voltage can be measured, for example, with an AC/DC/IR Hi-Pot tester.
- an AC/DC/IR Hi-Pot tester For example, a stainless steel mesh and a porous substrate are hot-pressed under the conditions of 90° C., 4 MPa, and 1 sec, and then the DC current is 0.5 mA, and the voltage is set to 100 V/s (voltage 3 kV, ramp up time 3 s). .
- the measurement is completed when the voltage rises and a short circuit occurs, and the voltage at that time is defined as the breakdown voltage.
- the evaluation of the short circuit occurrence rate is shown by the lower 1% of the specimens exhibiting a low breakdown voltage through Weibull analysis among the total number of specimens tested. It can be measured by checking the voltage.
- the porous substrate may be prepared by a method for manufacturing a polymer film, preferably a wet manufacturing method.
- the wet manufacturing method includes (S1) preparing the mixture, (S2) extruding the mixture and forming an extruded sheet, (S3) stretching the extruded sheet, (S4) removing the pore former, ( S5) heat setting of the extruded sheet.
- a type of polymer resin is appropriately selected according to the final physical properties of the separation membrane, and the polymer resin thus selected is mixed with a pore former.
- the polymer resin reference may be made to the description of the polymer resin of the porous substrate.
- the polymer resin may be a polyolefin-based polymer resin.
- the polyolefin-based polymer resin include one selected from polyethylene, such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene, or ultra-high molecular weight polyethylene, polypropylene, polybutylene, polypentene, or a combination of two or more thereof. may include
- the pore former is a material that is dispersed in a polymer, exhibits heterogeneity of a substrate prepared through extrusion, stretching, etc., and is subsequently removed from the substrate. Accordingly, the portion of the substrate where the pore former was located remains in the form of pores of the substrate.
- the pore former is preferably a liquid material in the extrusion process, but a material that maintains a solid state may be used.
- the pore-forming agent is an aliphatic hydrocarbon-based solvent such as liquid paraffin, paraffin oil, mineral oil or paraffin wax; vegetable oils such as soybean oil, sunflower oil, rapeseed oil, palm oil, palm oil, coconut oil, corn oil, grapeseed oil, cottonseed oil and the like; or a plasticizer such as a dialkyl phthalate.
- the plasticizer is di-2-ethylhexyl phthalate (DOP), di-butyl-phthalate (DBP), di-isononyl phthalate (di-isononyl phthalate, DINP) ), di-isodecyl phthalate (DIDP), butyl benzyl phthalate (BBP), and the like.
- liquid paraffin LP, also referred to as "liquid paraffin” is particularly preferred.
- the content of the pore-forming agent in the preparation of the separation membrane may be appropriately adjusted to achieve a desired level of porosity.
- the content of the pore former is high, but if it is contained in an excessively excessive amount, the strength of the finally produced substrate may be adversely affected. Therefore, the content of the pore former may be 1 wt% to 80 wt% with respect to 100 wt% of the total of the polymer resin and the pore former, and may be adjusted to 70 wt% or less, 60 wt% or less, or 50 wt% or less within the above range as necessary.
- the pore former is a polymer resin and a pore former. It may be included in the range of 1 wt% to 60 wt% relative to the total amount.
- the extruder is not particularly limited, and may be an extruder commonly used in the art, such as, but not limited to, an extruder having a T-die or a tubular die attached thereto.
- the extrusion process may be carried out at a conventional extrusion temperature, but it is preferably carried out at a temperature condition of 10° C. to 100° C. higher than the melting point of the polymer resin used.
- the extrusion process exceeds the above range too much, it is not preferable because the polymer resin is thermally degraded, making it difficult to form a film, and the physical properties of the prepared substrate are deteriorated.
- An extruded sheet can be obtained through this extrusion process.
- the extruded sheet is put into a stretching process.
- This stretching process is carried out through a stretching machine commonly used in the art.
- the stretching machine may be a sequentially biaxial stretching machine, but is not particularly limited thereto.
- the stretching process is carried out in the machine direction (MD), machine direction, longitudinal direction) and/or transverse direction (TD) direction.
- MD machine direction
- TD transverse direction
- the stretching process in all or one of these directions increases the tensile strength in the corresponding stretching direction.
- the separator of the present invention may be performed singly (eg, uniaxially), simultaneously or sequentially (eg, biaxially) stretching in the longitudinal direction (MD) and/or in the transverse direction (TD) in the stretching process.
- the temperature of the film in the stretching may be controlled to 100 °C to 130 °C, preferably 110 °C to 125 °C.
- the temperature of the film during stretching may be controlled in a range of 115°C to 121°C.
- the pore former is removed from the extruded sheet obtained above. Pore formers are removed by extraction and drying with a solvent. In addition, through this removal, the space occupied by the pore former is formed as pores.
- the solvent usable for extraction of the pore former may be any solvent capable of extracting the pore former, but preferably methyl ethyl ketone, methylene chloride, hexane, etc. with high extraction efficiency and fast drying. It is suitable.
- the solvent may be methylene chloride, such as methylene dichloride (MC).
- the extraction method all common solvent extraction methods such as an immersion method, a solvent spray method, and an ultrasonic method may be used individually or in combination.
- a step of heat-setting the substrate is performed, thereby finally obtaining a separation membrane having desired physical properties, porosity and air permeability.
- the heat setting step may be performed using a heating device capable of applying an appropriate temperature required for heat setting, for example, an oven.
- the previously dried film is finally subjected to heat setting in order to reduce the shrinkage of the final film by removing the residual stress.
- Heat setting is to remove residual stress by fixing the film and forcibly holding the film to be contracted by applying heat.
- a high heat setting temperature is advantageous for lowering the shrinkage rate, but if it is too high, the membrane is partially melted, thereby clogging the formed pores and lowering the transmittance.
- the preferred temperature of heat setting is preferably selected in a temperature range at which approximately 10 to 30 wt % of the crystalline portion of the film is melted. If the heat setting temperature is selected to be lower than the temperature at which about 10 wt% of the crystalline portion of the film melts, the reorientation of polyethylene molecules in the film is insufficient, and there is no effect of removing the residual stress of the film, and the film crystal If about 30 wt% of the portion is selected at a temperature higher than the melting temperature, the pores are blocked by the partial melting and the permeability is lowered.
- the porous substrate may be a single layer.
- the porous substrate may be a laminated film in which two or more films are laminated. At this time, at least one of the films included in the laminated film may be formed by the above-described method.
- the separation membrane may include a heat-resistant layer formed on at least one surface of the porous substrate.
- the heat-resistant layer includes an adhesive binder resin and inorganic particles, has a plurality of micropores therein, has a structure in which these micropores are connected, and is a porous material that allows gas or liquid to pass from one side to the other. It may have the structural characteristics of a layer.
- the binder resin and the inorganic particles in the heat-resistant layer may be included in a weight ratio of 1:99 to 30:70.
- the ratio may be appropriately adjusted within the above range, and for example, 100 wt% of the binder resin and inorganic particles may be 1 wt% or more, 5 wt% or more, or 10 wt% or more, and the inorganic particles may be 80 wt% or more. wt% or more, 85 wt% or more, 90 wt% or more, or 95 wt% or more.
- the heat-resistant layer preferably has a porous structure from the viewpoint of ion permeability.
- the heat-resistant layer may be formed by bonding inorganic particles through a binder resin, and pores may be formed by an interstitial volume between the inorganic particles.
- the interstitial volume is a space defined by inorganic particles substantially interfacing in a closed packed or densely packed structure of inorganic particles.
- the porosity of the heat-resistant layer is 30 vol% to 70 vol%, and the porosity within this range may be 35 vol% or more or 40 vol% or more, and at the same time or each independently 65 vol% or less or 60 vol%.
- the porosity may be 40 vol% to 60 vol%. If the porosity is 70 vol% or less, it is possible to secure mechanical properties that can withstand the pressing process of bonding with the electrode, and also, the surface opening ratio is not too high, so it is suitable for securing adhesion. On the other hand, if the porosity is 30 vol% or more, it is advantageous in terms of ion permeability.
- the porosity may be measured using BELSORP (BET equipment) manufactured by BEL JAPAN using an adsorbed gas such as nitrogen, or may be measured by a method such as mercury intrusion porosimetry.
- BELSORP BET equipment
- the true density of the electrode active material layer is determined from the obtained density (apparent density) of the obtained electrode (electrode active material layer) and the composition ratio of the materials included in the electrode (electrode active material layer) and the density of each component , and the porosity of the electrode active material layer may be calculated from the difference between the apparent density and the net density.
- the thickness of the heat-resistant layer may be 1 ⁇ m to 6 ⁇ m on one side of the porous substrate. If necessary within the above range, the thickness of the heat-resistant layer may be 2 ⁇ m or more, or 3 ⁇ m or more. Within the above numerical range, the adhesion to the electrode is excellent, and as a result, the cell strength of the battery is increased. On the other hand, when the thickness is 6 ⁇ m or less, it is advantageous in terms of cycle characteristics and resistance characteristics of the battery. From this point of view, the thickness is preferably 4 ⁇ m or less, and more preferably 3 ⁇ m or less.
- non-limiting examples of the binder resin that can be used for the heat-resistant layer include polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, and polyvinylidene fluoride- co-trichlorethylene), polymethylmethacrylate, polybutylacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate Polyethylene-co-vinyl acetate, polyethylene oxide, polyarylate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose , cyanoethyl sucrose (cyanoethylsucrose), pullulan (pullulan) and carboxyl methyl cellulose (carboxyl methyl cellulose) may be any one polymer resin selected from the group consisting of, or a mixture of two or more thereof.
- the binder resin may
- the inorganic particles that can be used in the heat-resistant layer are not particularly limited as long as they are electrochemically stable. That is, the inorganic particles that can be used in the present invention are not particularly limited as long as oxidation and/or reduction reactions do not occur in the operating voltage range of the applied electrochemical device (eg, 0 to 5V based on Li/Li + ).
- Non-limiting examples of the inorganic particles include BaTiO 3 , Pb(Zr,Ti)O 3 (PZT), b 1-x La x Zr 1-y Ti y O 3 (PLZT, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, Mg(OH) 2 , NiO, CaO, ZnO, ZrO 2 , SiO 2 , Y 2 O 3 , Al 2 O 3 , SiC, Al(OH) 3 , TiO 2 , aluminum peroxide, zinc tin hydroxide (ZnSn(OH) 6 ), tin-zinc oxides (Zn 2 SnO 4 , ZnSnO 3 ), antimony trioxide (Sb 2 O 3 ), antimony
- the inorganic particles may include inorganic particles having lithium ion transport capability.
- inorganic particles having such lithium ion transport ability include lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3) , lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), 14Li 2 O-9Al 2 O 3 -38TiO 2 -39P (LiAlTiP) x O y -based glass such as 2 O 5 (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 13), lithium lanthanide titanate (Li x La y TiO 3 , 0 ⁇ x ⁇ 2, 0 ⁇
- lithium germanium thiophosphate Li x Ge y P z S w , 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ w ⁇ 5
- lithium nitride such as Li 3 N (Li x N y , 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 2), Li 3 PO 4 -Li 2 S-SiS 2 , etc.
- SiS 2 based glass Li x P 2 S 5 series glass, such as Si y S z , 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 4
- LiI-Li 2 SP 2 S 5 etc. x ⁇ 3, 0 ⁇ y ⁇ 3, 0 ⁇ z ⁇ 7) or mixtures thereof.
- the average diameter (D 50 ) of the inorganic particles is not particularly limited, but is preferably in the range of 0.3 ⁇ m to 1 ⁇ m for the formation of a coating layer having a uniform thickness and an appropriate porosity. If it is less than 0.3 ⁇ m, the dispersibility of inorganic particles in the slurry prepared for preparing the heat-resistant layer may be reduced, and if it exceeds 1 ⁇ m, the thickness of the formed coating layer may increase.
- the method of forming the heat-resistant layer is, for example, as follows.
- a polymer solution is prepared by dissolving a binder resin in an appropriate organic solvent.
- a solvent it is preferable that the solubility index is similar to that of the binder polymer to be used, and the boiling point is low. This is to facilitate uniform mixing and subsequent solvent removal.
- the solvent include acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone ( N-methyl-2-pyrrolidone, NMP), cyclohexane, water, or a mixture thereof.
- inorganic particles are added and dispersed in the prepared polymer solution.
- the content ratio of the inorganic particles to the binder is as described above, and is appropriately adjusted in consideration of the thickness, pore size and porosity of the heat-resistant layer of the present invention finally manufactured.
- the inorganic particle slurry prepared above is applied to at least one side of the separation membrane and dried.
- a method of coating the slurry on the porous substrate is not particularly limited to any one method, and a conventional coating method known in the art may be used. For example, various methods such as dip coating, die coating, roll coating, comma coating, or a mixture thereof may be used.
- a drying auxiliary device such as a drying oven or hot air may be used within an appropriate range.
- the separator of the present invention can be manufactured by a method of separately preparing a heat-resistant layer and a porous substrate, stacking these sheets together, and combining them with thermocompression bonding or an adhesive.
- a method of obtaining a heat-resistant layer as an independent sheet the method of apply
- the present invention provides a secondary battery including the separator.
- the battery includes a negative electrode, a positive electrode, and a separator interposed between the negative electrode and the positive electrode, and the separator is a low-resistance separator having the above-described characteristics.
- the positive electrode includes a positive electrode current collector and a positive electrode active material layer including a positive electrode active material, a conductive material, and a binder resin on at least one surface of the current collector.
- the positive active material is a layered compound such as lithium manganese composite oxide (LiMn 2 O4, LiMnO 2 , etc.), lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ) or a compound substituted with one or more transition metals; Lithium manganese oxides such as Formula Li 1+x Mn 2-x O 4 (where x is 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , and LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); vanadium oxides such as LiV 3 O 8 , LiV 3 O 4 , V 2 O 5 , and Cu 2 V 2 O 7 ; Ni site-type lithium nickel oxide represented by the formula LiNi 1-x M x O 2 (where
- the negative electrode includes a negative electrode current collector and a negative electrode active material layer including a negative electrode active material, a conductive material and a binder resin on at least one surface of the current collector.
- the negative electrode may include, as an anode active material, carbon such as lithium metal oxide, non-graphitized carbon, and graphite-based carbon; LixFe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me' y O z (Me: Mn, Fe, Pb, Ge; Me': Al , B, P, Si, elements of Groups 1, 2, and 3 of the periodic table, halogen; lithium metal; lithium alloy; silicon-based alloys; tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2
- the conductive material is, for example, graphite, carbon black, carbon fiber or metal fiber, metal powder, conductive whisker, conductive metal oxide, activated carbon (activated carbon) and polyphenylene derivatives. It may be any one selected from the group consisting of or a mixture of two or more of these conductive materials. More specifically, natural graphite, artificial graphite, super-p, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, denka black, aluminum powder, nickel powder, oxide It may be one selected from the group consisting of zinc, potassium titanate and titanium oxide, or a mixture of two or more of these conductive materials.
- the current collector is not particularly limited as long as it has high conductivity without causing a chemical change in the battery, and for example, stainless steel, copper, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. A surface treated with carbon, nickel, titanium, silver, etc. may be used.
- binder resin a polymer commonly used for electrodes in the art may be used.
- binder resins include polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-cotrichlorethylene, polymethylmethacrylate ( polymethylmethacrylate, polyethylhexyl acrylate, polybutylacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate copolymer (polyethylene-co-vinyl acetate), polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, Cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan and carboxyl methyl cellulose cellulose) and the like, but is not limited thereto
- the electrode assembly prepared as described above may be charged in an appropriate case and an electrolyte may be injected to manufacture a battery.
- the electrolyte is a salt having the same structure as A + B - ,
- a + is Li + , Na + , K + contains alkali metal cations such as cations or a combination thereof
- B - is PF 6 - , BF 4 - , Cl - , Br - , I - , ClO 4 - , AsF 6 - , CH 3 CO 2 - , CF 3 SO 3 - , N(CF 3 SO 2 ) 2 - , C(CF 2 SO 2 ) 3 -
- the present invention provides a battery module including a battery including the electrode assembly as a unit cell, a battery pack including the battery module, and a device including the battery pack as a power source.
- the device include a power tool that is powered by an omniscient motor and moves; electric vehicles, including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooter); electric golf carts; and a power storage system, but is not limited thereto.
- a polyethylene resin composition was prepared by mixing the first polyethylene resin (Mw 250,000 g/mol) and the second polyethylene resin (Mw 800,000 g/mol).
- the composition had a molecular weight (Mw) of 497,000 g/mol and a PDI of 12.8.
- a porous substrate for a separator was obtained in the same manner as in Example.
- a polyethylene resin composition was prepared by mixing the first polyethylene resin (Mw 250,000 g/mol) and the second polyethylene resin (Mw 800,000 g/mol).
- the composition had a molecular weight (Mw) of 381,000 g/mol and a PDI of 10.5.
- Mw molecular weight
- PDI PDI
- Example 1 Example 2 Comparative Example 1 Comparative Example 2 Average pore size (nm) 25 30 27 28 Max pore size (nm) 32 45 65 77 Difference (nm) between the average pore size (m) and the maximum pore size (M) 7 15 38 49 Half width (nm) 0.8 2.6 4.2 5.1 Porosity (vol%) 45 45 45 45 45 45 45 45 45 BET surface area (m 2 /g) 47 39 43 41 Permeability change rate (%) 10 11 67 86 Thickness strain (%) 4 6 14 18 Insulation breakdown voltage (V) 1590 1,323 494 475
- the bubble point may represent the maximum diameter of the pores, and the point where the wet sample curve and the dry sample curve meet may represent the minimum diameter of the pores.
- a point at which the aeration curve of the 1/2 dry sample and the wet sample curve, which is a value corresponding to 1/2 of the value of the aeration curve of the dry sample, may represent the average value of the pore diameter (see FIG. 4 ).
- the porosity was calculated through [Equation 1] and [Equation 2] below.
- Air permeability was checked for the porous substrates obtained in each Example and Comparative Example.
- the air permeability was measured according to the Fraser test method according to ASTM D 737 regulations, and an Asahi seico EG01-55-1MR air permeation tester was used.
- Measuring pressure 0.5 kg/cm2, cylinder pressure: 2.5 kg/cm2, set time: 10 seconds
- the initial thickness of the porous substrate and the thickness after pressing were measured using a contact thickness meter. Measurements were performed at intervals of 5 mm over a distance of 30 cm along the TD direction of the porous substrate. Then, the measurement along the TD direction was performed 5 times at different MD positions, and the arithmetic mean was taken as the thickness of the porous substrate. On the other hand, the thickness change rate (%) of each porous substrate was calculated through [Equation 4] below.
- the thickness change rate of the porous substrate of Example 1 was confirmed to be lower than those of Comparative Examples 1 and 2.
- Example 2 For each Example and Comparative Example, 30 specimens were prepared, respectively, and their withstand voltage characteristics were evaluated.
- the stainless steel mesh and the porous substrate were hot-pressed under the conditions of 90° C., 4 MPa, and 1 sec, and then DC current was set to 0.5 mA, and the voltage was set to 100 V/s (voltage 3 kV, ramp up time 3 s).
- the test started the measurement was completed when a short circuit occurred in each specimen as the voltage was increased, and the voltage at that time was measured as the breakdown voltage.
- the voltages indicated by the lower 1% specimens exhibiting low breakdown voltage were measured and summarized in Table 2.
- the size of the pores is small and uniform, and thus, the withstand voltage characteristic and the thickness deformation rate are excellent compared to the porous substrate according to the comparative example.
- the polydispersity index was calculated according to Equation 5 below.
- Polydispersity index number average molecular weight (Mn) / weight average molecular weight (Mw)
- the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC, PL GPC220, Agilent Technologies), and the measurement conditions were set as follows.
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Abstract
Description
실시예 1 | 실시예 2 | 비교예 1 | 비교예 2 | |
평균 기공 크기(nm) | 25 | 30 | 27 | 28 |
Max pore size (nm) | 32 | 45 | 65 | 77 |
기공 평균 크기(m)와 최대 기공 크기(M)의 차이 (nm) | 7 | 15 | 38 | 49 |
반가폭 (nm) | 0.8 | 2.6 | 4.2 | 5.1 |
기공도(vol%) | 45 | 45 | 45 | 45 |
BET 표면적(m2/g) | 47 | 39 | 43 | 41 |
통기도 변화율(%) | 10 | 11 | 67 | 86 |
두께 변형율(%) | 4 | 6 | 14 | 18 |
절연파괴전압 (V) | 1590 | 1,323 | 494 | 475 |
Claims (13)
- 분리막용 다공성 기재이며,상기 다공성 기재는 폴리올레핀계 고분자 수지를 포함하고, 상기 고분자 수지는 폴리에틸렌 및/또는 폴리프로필렌을 포함하며, 상기 기재는 내부에 복수의 기공을 포함하는 다공성 특성을 가지고,이의 기공도가 30vol% 내지 60vol%이며,상기 기공의 산포는 pore side distribution의 분포를 통해 측정된 가우시안 기공 분포의 반가폭(HWHM)의 값이 4.0nm 이하인 것인 분리막용 다공성 기재.
- 제1항에 있어서,상기 기공의 산포는 반가폭의 값이 3.0nm이하인 것인 분리막용 다공성 기재.
- 제1항에 있어서,상기 기공의 산포는 반가폭의 값이 2.0nm이하인 것인 분리막용 다공성 기재.
- 제1항에 있어서,최대 기공 크기(Mps)와 평균 기공 크기(mps)의 차가 30nm이하인 것인 분리막용 다공성 기재.
- 제1항에 있어서,최대 기공 크기(Mps)와 평균 기공 크기(mps)의 차가 20nm이하인 것인 분리막용 다공성 기재.
- 제4항에 있어서,상기 평균 기공 크기(mps)는 10nm 내지 100nm인 것인 분리막용 다공성 기재.
- 제4항에 있어서,상기 평균 기공 크기(mps)는 20nm 내지 30nm인 것인 분리막용 다공성 기재.
- 제1항에 있어서,상기 다공성 기재는 BET가 20m2/g 내지 60m2/g인 것인 분리막용 다공성 기재.
- 제1항에 있어서,두께가 5㎛ 내지 20㎛인 분리막용 다공성 기재.
- 제1항에 있어서,상기 고분자 수지는 고분자 수지 100wt% 대비 폴리올레핀계 수지를 90wt% 이상 포함하는 것인 분리막용 다공성 기재.
- 제10항에 있어서,상기 폴리올레핀계 수지는 PDI(poly dispersity index)의 값이 2.5 내지 6.5 인 것인 분리막용 다공성 기재.
- 제1항 내지 제11항 중 어느 한 항에 따른 분리막용 다공성 기재 및 상기 다공성 기재의 표면의 일측면 또는 양면에 형성된 내열층을 포함하며,상기 내열층은 바인더 수지와 무기물 입자를 포함하는 것인 전기화학소자용 분리막.
- 음극, 양극 및 상기 음극과 양극 사이에 개재된 분리막을 포함하며 상기 분리막은 제12항에 따른 것인 전기화학소자.
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US18/036,748 US20230411794A1 (en) | 2021-05-07 | 2022-05-06 | Porous substrate for separator and separator for electrochemical device comprising same |
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KR20220152171A (ko) | 2022-11-15 |
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